EP0716072A1 - Polyéthercarboxylates concentrés à écoulement libre - Google Patents

Polyéthercarboxylates concentrés à écoulement libre Download PDF

Info

Publication number: EP0716072A1
Authority: EP; European Patent Office
Prior art keywords: polyether; carbon atoms; alkyl; temperatures; polyether carboxylate
Prior art date: 1994-12-08
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP95116082A

Other languages

German (de)

English (en)

Other versions

EP0716072B1 (fr

Inventor

Michael Dr. Brock

Meinolf Enneking

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Sasol Germany GmbH

Wintershall Dea International AG

Original Assignee

Huels AG

Chemische Werke Huels AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1994-12-08

Filing date

1995-10-12

Publication date

1996-06-12

1995-10-12 Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG

1996-06-12 Publication of EP0716072A1 publication Critical patent/EP0716072A1/fr

1998-01-07 Application granted granted Critical

1998-01-07 Publication of EP0716072B1 publication Critical patent/EP0716072B1/fr

2015-10-12 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 56
229920000570 polyether Polymers 0.000 title claims abstract description 56
150000007942 carboxylates Chemical class 0.000 title claims abstract description 38
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
-1 carboxylate salt Chemical class 0.000 claims abstract description 21
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 14
150000001735 carboxylic acids Chemical class 0.000 claims abstract description 11
238000006386 neutralization reaction Methods 0.000 claims abstract description 10
125000002947 alkylene group Chemical group 0.000 claims abstract description 9
239000003513 alkali Substances 0.000 claims abstract description 6
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 4
239000005977 Ethylene Substances 0.000 claims abstract description 4
QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 3
125000004432 carbon atom Chemical group C* 0.000 claims description 26
239000012141 concentrate Substances 0.000 claims description 20
238000000034 method Methods 0.000 claims description 9
230000009969 flowable effect Effects 0.000 claims description 8
150000001875 compounds Chemical class 0.000 claims description 6
238000002360 preparation method Methods 0.000 claims description 5
WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims description 4
239000012459 cleaning agent Substances 0.000 claims description 3
239000003599 detergent Substances 0.000 claims description 3
239000003995 emulsifying agent Substances 0.000 claims description 3
229910052783 alkali metal Inorganic materials 0.000 claims description 2
150000001340 alkali metals Chemical class 0.000 claims description 2
229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
150000001342 alkaline earth metals Chemical class 0.000 claims description 2
239000002270 dispersing agent Substances 0.000 claims description 2
238000005496 tempering Methods 0.000 claims 3
125000000217 alkyl group Chemical group 0.000 abstract description 3
238000010438 heat treatment Methods 0.000 abstract 2
125000002877 alkyl aryl group Chemical group 0.000 abstract 1
239000012530 fluid Substances 0.000 abstract 1
230000003472 neutralizing effect Effects 0.000 abstract 1
FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
239000011780 sodium chloride Substances 0.000 description 11
239000000203 mixture Substances 0.000 description 5
229940077464 ammonium ion Drugs 0.000 description 4
238000004519 manufacturing process Methods 0.000 description 4
239000003921 oil Substances 0.000 description 3
GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
239000008346 aqueous phase Substances 0.000 description 2
RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
238000005259 measurement Methods 0.000 description 2
230000007935 neutral effect Effects 0.000 description 2
150000003839 salts Chemical class 0.000 description 2
229910052708 sodium Inorganic materials 0.000 description 2
239000011734 sodium Substances 0.000 description 2
159000000000 sodium salts Chemical class 0.000 description 2
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
239000013543 active substance Substances 0.000 description 1
239000000654 additive Substances 0.000 description 1
150000001298 alcohols Chemical class 0.000 description 1
150000001447 alkali salts Chemical class 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
238000009826 distribution Methods 0.000 description 1
125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
230000001804 emulsifying effect Effects 0.000 description 1
239000006260 foam Substances 0.000 description 1
239000012535 impurity Substances 0.000 description 1
239000007788 liquid Substances 0.000 description 1
229910052749 magnesium Inorganic materials 0.000 description 1
239000011777 magnesium Substances 0.000 description 1
VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
239000000347 magnesium hydroxide Substances 0.000 description 1
229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
239000000395 magnesium oxide Substances 0.000 description 1
CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
229910052700 potassium Inorganic materials 0.000 description 1
239000011591 potassium Substances 0.000 description 1
239000002453 shampoo Substances 0.000 description 1
239000000344 soap Substances 0.000 description 1
FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
229910001415 sodium ion Inorganic materials 0.000 description 1
239000007787 solid Substances 0.000 description 1
125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
239000000725 suspension Substances 0.000 description 1
238000003786 synthesis reaction Methods 0.000 description 1
GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups

Definitions

the invention relates to concentrated polyether carboxylates flowable at 40 ° C., a process for their preparation and their use as dispersants and emulsifiers in the detergent and cleaning agent sector.
salts of polyether carboxylic acids in soap oils Fette Wachsen 109 (1983), 353 are particularly kind to the skin and are therefore increasingly used in shampoos, shower and foam baths.
the polyether carboxylates are notable for exceptional hardness stability and very good dispersing and emulsifying properties, so that they can also be used in the detergent and cleaning agent sector and as technical emulsifiers.
polyether carboxylates Essentially two processes are described for the production of polyether carboxylates. They can be prepared by selective oxidation of the terminal primary hydroxyl group of an oxyethylate to a carboxyl group under basic conditions (DE-34 46 561). However, the synthesis of the polyether carboxylates by carboxymethylation of the hydroxyl group of the oxethylate with sodium chloroacetate in the presence of sodium hydroxide is more widespread. The sodium salts of the corresponding polyether carboxylic acids are obtained, which are contaminated as raw products with the starting products and sodium chloride.
the disruptive sodium chloride can according to Kosswig and Stache, Die Tenside, Carl Hanser Verlag Kunststoff ⁇ Vienna, 1993, p. 123, after acidifying z. B. be separated with sulfuric acid.
the sodium carboxylate is converted into the polyether carboxylic acid which, because of its insolubility in water, can settle over the acidic, aqueous phase and can be separated off practically free of chloride ions.
the sodium chloride remains in the aqueous phase.
the polyether carboxylic acids obtained in this way are water-clear and easily movable liquids which, in addition to a few% by weight of residual water and any unreacted oxyethylate present, contain no other noteworthy impurities.
EP-0 344 442 describes the production of pumpable products with an active content of more than 70% by weight, but to which short-chain alcohols have to be added as thinners. However, their presence is generally not desired by processors of such products.
the object of the present invention was therefore to develop a process for the production of largely free of sodium chloride, free-flowing and concentrated polyether carboxylates, to which no alcohol and also no other additives for lowering the viscosity have to be added.
the object is achieved in that concentrated polyether carboxylic acids are neutralized with corresponding alkaline compounds at 40 to 100 ° C to polyether carboxylates and the polyether carboxylate salt is heated at 40 to 100 ° C for up to 12 hours.
a vacuum of 1 to 800 mbar, preferably 10 to 600 mbar, can be applied and, if appropriate, the water can be at least partially removed from the system.
the polyether carboxylate concentrates thus obtained have a water content of 0 to 20% by weight.
the concentration of polyether carboxylates is 50 to 100% by weight, preferably 65 to 100% by weight.
Oxethylate which has not been converted into polyether carboxylate can contain up to 50% by weight.
the total solids content is up to 100% by weight.
Flowability at 40 ° C in the sense of this invention is understood to mean solutions or suspensions which, at 40 ° C, have a viscosity of less than 50,000 mPa ⁇ s at a shear rate of 10 s ⁇ 1 with a Haake rotary viscometer, NV or SV-DIN.
R is, for example, decyl, lauryl, isotridecyl, myristyl, palmityl, stearyl or nonylphenyl.
R is preferably alkyl having 10 to 16 carbon atoms.
A is preferably ethylene and / or propylene. In a particularly preferred embodiment, A is ethylene.
M examples are potassium, sodium, ammonium, magnesium or substituted ammonium ions such as trimethylammonium, triethanolammonium, mono-, di- and triisopropanolammonium.
M is preferably the sodium ion.
the neutralization is therefore carried out with the appropriate alkaline compounds, such as. B. sodium hydroxide solution, potassium hydroxide solution, magnesium oxide, magnesium hydroxide or trimethylamine.
the polyether carboxylate concentrates according to the invention have a high content of active substance, are practically free of sodium chloride and flowable at 40 ° C. "Practically free of sodium chloride” denotes a sodium chloride content of at most 0.5% by weight.
samples 1 to 8 are flowable at 40 ° C., sample 9 not according to the invention is not.
Example 1 Viscosity [mPa ⁇ s] Sample 1 (water content 1.2% by weight) 300 Sample 2 (water content 4% by weight) 300 Sample 3 (water content 6% by weight) 300 Sample 4 (water content 8% by weight) 300 Sample 5 (water content 10% by weight) 300 Sample 6 (water content 12% by weight) 300 Sample 7 (water content 15% by weight) 2,500 Sample 8 (water content 22% by weight) 50,000
Samples 1 to 7 are flowable at 40 ° C., sample 8 not according to the invention is not.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Polyethers (AREA)
Detergent Compositions (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

EP95116082A 1994-12-08 1995-10-12 Polyéthercarboxylates concentrés à écoulement libre Expired - Lifetime EP0716072B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE4443664		1994-12-08
DE4443664A DE4443664A1 (de)	1994-12-08	1994-12-08	Konzentrierte fließfähige Polyethercarboxylate

Publications (2)

Publication Number	Publication Date
EP0716072A1 true EP0716072A1 (fr)	1996-06-12
EP0716072B1 EP0716072B1 (fr)	1998-01-07

Family

ID=6535241

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP95116082A Expired - Lifetime EP0716072B1 (fr)	1994-12-08	1995-10-12	Polyéthercarboxylates concentrés à écoulement libre

Country Status (2)

Country	Link
EP (1)	EP0716072B1 (fr)
DE (2)	DE4443664A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2003008510A1 (fr) *	2001-07-19	2003-01-30	Clariant Gmbh	Dispersions pigmentaires basees sur l'eau et sur l'acrylate
WO2008135482A3 (fr) *	2007-05-05	2008-12-31	Basf Se	Nouveaux liquides ioniques

Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0331085A2 (fr) *	1988-02-29	1989-09-06	Montefibre S.p.A.	Dérivés polyoxyalkylène étheriques de sels et d'esters d'acides carboxyliques

1994
- 1994-12-08 DE DE4443664A patent/DE4443664A1/de not_active Withdrawn
1995
- 1995-10-12 EP EP95116082A patent/EP0716072B1/fr not_active Expired - Lifetime
- 1995-10-12 DE DE59501215T patent/DE59501215D1/de not_active Expired - Fee Related

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0331085A2 (fr) *	1988-02-29	1989-09-06	Montefibre S.p.A.	Dérivés polyoxyalkylène étheriques de sels et d'esters d'acides carboxyliques

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
WO2003008510A1 (fr) *	2001-07-19	2003-01-30	Clariant Gmbh	Dispersions pigmentaires basees sur l'eau et sur l'acrylate
US7285592B2 (en)	2001-07-19	2007-10-23	Clariant Produkte (Deutschland) Gmbh	Pigments dispersions based on water and acrylate
CZ307388B6 (cs) *	2001-07-19	2018-07-18	Clariant Produkte (Deutschland) Gmbh	Vodná pigmentová disperze na bázi akrylátů
WO2008135482A3 (fr) *	2007-05-05	2008-12-31	Basf Se	Nouveaux liquides ioniques
US20100137175A1 (en) *	2007-05-05	2010-06-03	Basf Se	Novel ionic liquids
US8461382B2 (en)	2007-05-05	2013-06-11	Basf Se	Ionic liquids
CN101675023B (zh) *	2007-05-05	2014-10-29	巴斯夫欧洲公司	包含聚醚羧酸根作为阴离子的离子液体，其制备方法及其用途

Also Published As

Publication number	Publication date
DE59501215D1 (de)	1998-02-12
EP0716072B1 (fr)	1998-01-07
DE4443664A1 (de)	1996-06-13

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Publication	Publication Date	Title
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